Method for hydrophobing textile materials

ABSTRACT

The process for finishing textile materials by treatment with at least one aqueous liquor which comprises at least one organic polymer and at least one organic or inorganic solid in particulate form, wherein the organic or inorganic solid or solids are present in the liquor in a fraction of at least 5.5 g/l.

The present invention relates to a process for finishing textilematerials by treatment with at least one aqueous liquor which comprisesat least one organic polymer and at least one organic or inorganic solidin particulate form, wherein the organic or inorganic solid or solidsare present in the liquor in a fraction of at least 5.5 g/l.

The finishing of textiles is a field of growing commercial importance.It is particularly interesting to finish textiles to render them waterand soil repellent. Modern measures utilize in some cases the so-calledLotus-Effect® and confer water-repellent performance on textiles byapplying a rough surface.

WO 96/04123 describes self-cleaning surfaces which have an artificialsurface structure which has elevations and depressions, the structurebeing characterized by its structural parameters in particular. Thestructures are prepared for example by embossing a structure onto athermoplastically formable hydrophobic material or by applying Teflonpowder to a surface which has been treated with UHU®. U.S. Pat. No.3,354,022 discloses similarly prepared water-repellent surfaces.

EP-A 0 933 388 discloses processes for preparing structured surfacesthat comprise first preparing a negative mold by photolithography, usingthis mold to emboss a plastics film and then hydrophobicizing theembossed plastics film with fluorinated alkylsilanes.

However, the methods described above are unsuitable for soil- andwater-repellent finishing of textiles.

WO 02/84013 proposes hydrophobicizing fibers, composed of polyester forexample, by pulling them through a hot decalin bath at 80° C. in which1% of Aerosil® 8200 hydrophobicized silica gel has been suspended.

WO 02/84016 proposes hydrophobicizing woven polyester fabric by pullingit through a bath of hot DMSO (dimethyl sulfoxide) at 50° C. in which 1%of Aeroperl®8200 hydrophobicized silica gel has been suspended.

The two hydrophobicization methods have the common feature that thesolvent is selected such that the fibers are partially dissolved. Thisrequires using large amounts of organic solvent, and this is undesirablein many cases. Moreover, treatment with organic solvents can have aneffect on fiber mechanical properties.

WO 01/75216 proposes rendering textile fibers and fabrics water and soilrepellent by providing them with a two-component layer, of which one isa dispersion medium and the other is a colloid for example. Thefinishing process described in WO 01/75216 provides finishing layers inwhich the colloids are anisotropically dispersed in the dispersionmedium in that the colloids are observed to become concentrated at theboundary layer between the finishing layer and the surrounding surface.The process utilizes finishing liquors which contain up to 5 g/l ofAerosil 812 S.

However, textiles finished by the process described in WO 01/75216 lacksatisfactory mechanical strength in many cases.

It is an object of the present invention to provide a process forfinishing textile materials which is free of the above-indicateddisadvantages and which also provides a very good water- andsoil-repellent performance. It is a further object of the presentinvention to provide soil- and water-repellent textiles. It is a furtherobject of the present invention to provide liquors for soil- andwater-repellent finishing of textile materials.

We have found that this object is achieved by the process defined at thebeginning.

Textile materials for the purposes of the present invention are fibers,roving, yarn, thread on the one hand and textile fabrics on the othersuch as for example wovens, knits, nonwovens and garments. Particularpreference is given to textile fabrics used for manufacturing outdoortextiles for example. Examples are sails, umbrellas, tarpaulins,groundsheets, tablecloths, awnings and furniture covers for example forchairs, swings or benches.

Textile materials for the purposes of the present invention can consistof different substances. Examples are natural fibers and syntheticfibers and also blend fibers. Examples of natural fibers are silk, wooland cotton. Examples of synthetic fibers are polyamide, polyester,polypropylene, polyacrylonitrile, polyethylene terephthalate andviscose. Similarly, modified natural fibers can be coated according tothe process of the present invention, for example cellulose acetate.

The process of the present invention utilizes at least one aqueousliquor. Aqueous liquor for the purposes of the present inventioncomprehends liquors which may comprise at least 5% by weight of water.The water content of aqueous liquors is preferably at least 25% byweight, more preferably at least 50% by weight and most preferably atleast 75% by weight. The maximum water content is 99% by weight,preferably 97% by weight and more preferably 95% by weight.

Aqueous liquors used in this invention can comprise organic solvents,for example methanol, ethanol, isopropanol, acetone, methyl ethylketone, methyl isobutyl ketone, ethylene glycolmono-n-butyl ether,ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol,n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers,as well as water. Organic solvents can account for 1-50% by weight andpreferably 2-25% by weight of the aqueous liquor used in this invention.

At least one of the liquors used in the process of this inventioncomprises at least one organic polymer. Organic polymers can serve as abinder. The action of a binder can be brought about for example by theorganic polymer forming a film which binds the particles to each otherand to the textile material to be coated.

In one embodiment of the present invention, at least one organic polymercomprises polymers or copolymers of ethylenically unsaturatedhydrophobic monomers which have a 25° C. solubility in water of lessthan 1 g/l. In copolymers, hydrophobic monomers account for at least 50%by weight and preferably at least 75% by weight of the copolymer.

Preferred monomers are selected from the groups of the

-   C₂-C₂₄-olefins, especially α-olefins of 2 to 24 carbon atoms, for    example ethylene, propylene, 1-butene, isobutene, 1-hexene,    1-octene, 1-decene, 1-dodecene, 1-hexadecene or 1-octadecene;-   styrenics, for example styrene, α-methylstyrene, cis-stilbene,    trans-stilbene, diolefins such as for example 1,3-butadiene,    cyclopentadiene, chloroprene or isoprene, C₅-C₁₈-cycloolefins such    as for example cyclopentene, cyclohexene, norbornene, dimeric    cyclopentadiene,-   vinyl esters of linear or branched C₁-C₂₀-alkanecarboxylic acids    such as for example vinyl acetate, vinyl propionate, vinyl    n-butyrate, vinyl n-hexanoate, vinyl n-octanoate, vinyl laurate and    vinyl stearate,-   (meth)acrylic esters of C₁-C₂₀-alcohols, for example    methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate,    isopropyl(meth)acrylate, n-butyl(meth)acrylate,    isobutyl(meth)acrylate, tert-butyl(meth)acrylate,    2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate,    n-decyl(meth)acrylate, n-dodecyl(meth)acrylate,    n-eicosyl(meth)acrylate-   and most preferably from the groups of the halogenated monomers and    the monomers having siloxane groups.

Halogenated monomers include chlorinated olefins such as for examplevinyl chloride and vinylidene chloride.

Most particularly preferred halogenated monomers are fluorous olefinssuch as for example vinylidene fluoride, trifluorochloroethylene,tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated orperfluorinated C₃-C₁₁-carboxylic acids as described for example in U.S.Pat. No. 2,592,069 and U.S. Pat. No. 2,732,370 (meth)acrylic esters offluorinated or perfluorinated alcohols such as for example fluorinatedor perfluorinated C₃-C₁₄-alkyl alcohols, for example (meth)acrylateesters of HO—CH₂—CH₂—CF₃, HO—CH₂—CH₂—C₂F₅, HO—CH₂—CH₂-n-C₃F₇,HO—CH₂—CH₂-iso-C₃F₇, HO—CH₂—CH₂-n-C₄F₉, HO—CH₂—CH₂-n-C₆F₁₃,HO—CH₂—CH₂-n-C₈F₁₇, HO—HC₂—CH₂-n-C₁₀F₂₁, HO—CH₂—CH₂-n-C₁₂F₂₅, describedfor example in U.S. Pat. No. 2,642,416, U.S. Pat. No. 3,239,557, BR1,118,007, U.S. Pat. No. 3,462,296.

Similarly, copolymers of for example glycidyl (meth)acrylate with estersof the formula I

-   where:-   R¹ is hydrogen, CH₃, C₂H₅,-   R² is CH₃, C₂H₅,-   x is an integer from 4 to 12 and most preferably from 6 to 8-   y is an integer from 1 to 11 and preferably from 1 to 6,-   or glycidyl(meth)acrylate with vinyl esters of fluorinated    carboxylic acids.

Useful copolymers further include copolymers of (meth)acrylic esters offluorinated or perfluorinated C₃-C₁₂-alkyl alcohols such as for exampleHO—CH₂—CH₂—CF₃, HO—CH₂—CH₂—C₂F₅, HO—CH₂—CH₂-n-C₃F₇, HO—CH₂—CH₂-iso-C₃F₇,HO—CH₂—CH₂-n-C₄F₉, HO—CH₂—CH₂-n-C₅F₁₁, HO—CH₂—CH₂-n-C₆F₁₃,HO—CH₂—CH₂-n-C₇F₁₅;

-   with (meth)acrylic esters of nonhalogenated C₁-C₂₀-alcohols, for    example methyl(meth)acrylate, ethyl(meth)acrylate,    n-butyl(meth)acrylate, n-propyl(meth)acrylate,    2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate,    n-decyl(meth)acrylate, n-dodecyl(meth)acrylate,    n-eicosyl(meth)acrylate.

An overview of suitable fluorinated polymers and copolymers is given forexample in M. Lewin et al., Chemical Processing of Fibers and Fabrics,Part B, Volume 2, Marcel Dekker, New York (1984), pages 172 ff. andpages 178-182.

Further suitable fluorinated polymers are disclosed for example in DE199 120 810.

From the group of the olefins having siloxane groups there may bementioned for example olefins of the general formulae II a to II c

-   where:-   R³ is selected from-   C₁-C₁₈-alkyl, for example methyl, ethyl, n-propyl, isopropyl,    n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,    sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,    isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl,    n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl; preferably    C₁-C₆-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,    isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,    neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl,    sec-hexyl, more preferably C₁-C₄-alkyl such as methyl, ethyl,    n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and tert-butyl    and especially methyl.-   C₆-C₁₄-Aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,    2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,    4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and    2-naphthyl, more preferably phenyl C₃-C₁₂-cycloalkyl, for example    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,    cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl;    preference is given to cyclopentyl, cyclohexyl and cycloheptyl or    Si(CH₃)₃.-   R¹ is as defined above.-   n is an integer from 0 to 6 and especially from 1 to 2;-   m is an integer from 2 to 10 000 and especially up to 100.

Useful polymers further include: polyethers such as for examplepolyethylene glycol, polypropylene glycol, polybutylene glycols,polytetrahydrofuran; polycaprolactone, polycarbonates, polyvinylbutyral,

-   partly aromatic polyesters formed from aliphatic or aromatic    dicarboxylic acids and/or aliphatic or aromatic dialcohols, for    example-   polyesters formed from aliphatic dialcohols having 2 to 18 carbon    atoms such as for example ethylene glycol, propanediol,    1,4-butanediol, 1,6-hexanediol, 1,8-octanediol or bisphenol A, and    aliphatic dicarboxylic acids having 3 to 18 carbon atoms such as for    example succinic acid, glutaric acid, adipic acid and    α,ω-decanedicarboxylic acid; polyesters formed from terephthalic    acid and aliphatic dialcohols having 2 to 18 carbon atoms such as    for example ethylene glycol, propanediol, 1,4-butanediol,    1,6-hexanediol or 1,8-octanediol.

Polyesters mentioned above can be terminated for example withmonoalcohols such as for example 4 to 12 carbon atoms, for examplen-butanol, n-hexanol, n-octanol, n-decanol or n-dodecanol.

Polyesters mentioned above can be terminated for example withmonocarboxylic acids such as for example stearic acid.

Useful polymers further include melamine-formaldehyde resins,urea-formaldehyde resins, N,N-dimethylol-4,5-dihydroxyethyleneureaswhich may be etherified with C₁-C₅ alcohols.

The molecular weight of the organic polymer or polymers can be selectedwithin wide limits. The weight average molecular weight can be in therange from 1000 to 10 000 000 g/mol and preferably in the range from2500 to 5 000 000 g/mol, determined by at least one of the followingmethods: light scattering, gel permeation chromatography (GPC),viscometry. When a polymer from the group of the polyolefins is used,for example polyethylene, polypropylene or polyisobutylene, and alsocopolymers of ethylene with propylene, butylene or 1-hexene, themolecular weight will advantageously be in the range from 30 000 to 5000 000 g/mol.

The width of the molecular weight distribution is not critical as suchand can be in the range from 1.1 to 20. It is customarily in the rangefrom 2 to 10.

In one embodiment of the present invention, the fraction of the organicpolymer or polymers described above is at least 0.1 g/l of the liquor,preferably at least 1 g/l and more preferably at least 10 g/l. Themaximum fraction is for example 500 g/l, preferably 250 g/l and morepreferably 100 g/l.

In one embodiment of the present invention, the organic polymer orpolymers are not soluble in the liquor, not soluble meaning in thecontext of with organic polymers for the purposes of the presentinvention that the room temperature solubility in the liquor is lessthan 1 g/l and more preferably less than 0.1 g/l.

One embodiment of the present invention comprises using at least twodifferent organic polymers.

In one embodiment of the present invention, at least one organic polymercan be present in the form of particles having a measure of centraltendency particle diameter in the range from 0.1 to 50 μm, preferablyfrom 0.5 to 30 μm and more preferably up to 20 μm (median value, numberaverage).

At least one aqueous liquor used in the process of this inventioncomprises at least one hydrophobic solid in particulate form thatdiffers from the polymer or polymers described above, in a fraction ofat least 5.5 g/l, preferably at least 7 g/l and more preferably at least10 g/l. When it is desired to use at least two hydrophobic solids inparticulate form, then it is preferable for at least one to be presentin a fraction of at least 5.5 g/l. The maximum fraction of thehydrophobic solid or solids in particulate form can be 150 g/l in total.The hydrophobic solid in particulate form can be inorganic or organic innature; preferably, it is inorganic.

Examples of suitable materials are polyethylene, polypropylene,polyisobutylene and polystyrene and also copolymers thereof with eachother or with one or more further olefins such as for example styrene,methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate,butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,maleic anhydride or N-methylmaleimide. A preferred polyethylene orpolypropylene is described for example in EP-A 0 761 696.

Particularly useful materials include inorganic materials, especiallysolid inorganic oxides, carbonates, phosphates, silicates or sulfates ofgroups 3 to 14 of the periodic table, for example calcium oxide, silicondioxide or aluminum oxide, calcium carbonate, calcium sulfate or calciumsilicate, of which aluminum oxide and silicon dioxide are preferred.Particular preference is given to silicon dioxide in its silica gelform. Very particular preference is given to pyrogenic silica gels.Solid inorganic oxides can be hydrophobicized thermally by heating to400-800° C. or preferably through physisorbed or chemisorbed organic ororganometallic compounds. For this, particles are reacted prior to thecoating step with, for example, organometallics which comprise at leastone functional group, for example alkyllithium compounds such asmethyllithium, n-butyllithium or n-hexyllithium; or silanes such as forexample hexamethyldisilazane, octyltrimethoxysilane and especiallyhalogenated silanes such as trimethylchlorosilane ordichlorodimethylsilane.

Hydrophobic in the context of the hydrophobic solid or solids inparticulate form is to be understood as meaning that its solubility isbelow 1 g/l and preferably below 0.3 g/l (determined at roomtemperature).

Inorganic solids can preferably be porous in nature. The porousstructure is best characterized in terms of the BET surface areameasured in accordance with German standard DIN 66131. Inorganic solidsused can preferably a BET surface area in the range from 5 to 1000 m²/g,preferably in the range from 10 to 800 m²/g and more preferably in therange from 20 to 500 m²/g.

In one embodiment of the present invention, at least one of thehydrophobic solids is present in particulate form. The measure ofcentral tendency particle diameter (median value, number average) is atleast 1 nm, preferably at least 3 nm and more preferably at least 6 nm.The maximum particle diameter (median value, number average) is 350 nmand preferably 100 nm. The particle diameter can be measured usingcommonly used methods such as for example transmission electronmicroscopy.

The weight ratio of organic polymer to organic or inorganic solid inparticulate form is generally in the range from 9:1 to 1:9, preferablyin the range from 4:1 to 1:4 and more preferably in the range from 7:3to 4:6.

In one embodiment of the present invention, at least one of thehydrophobic solids is present in the form of spherical particles, whichis intended to comprehend particulate solids where at least 75% byweight and preferably at least 90% by weight is present in sphericalform while other particles are present in granular form.

In one embodiment of the present invention, at least one of thehydrophobic solids can form agglomerates. When one or more hydrophobicsolids are present in the form of agglomerates, which can consist offrom 2 to several thousand primary particles and which in turn can havea spherical form, the particulars concerning particle form and sizerelate to primary particles.

At least one liquor used in the process of this invention can compriseat least one surface-active agent selected for example from the group ofthe ionic and nonionic emulsifiers.

Useful nonionic emulsifiers include for example ethoxylated mono-, di-and trialkylphenols (degree of ethoxylation: 3-50, alkyl radical:C₄-C₁₂) and also ethoxylated fatty alcohols (degree of ethoxylation:3-80; alkyl radical: C₈-C₃₆). Examples thereof are the Lutensol® gradesfrom BASF Aktiengesellschaft or the Triton® grades from Union Carbide.

Useful anionic emulsifiers include for example alkali metal and ammoniumsalts of alkyl sulfates (alkyl radical: C₈-C₁₂), of sulfuric monoestersof ethoxylated alkanols (degree of ethoxylation: 4-30, alkyl radical:C₁₂-C₁₈) and of ethoxylated alkylphenols (degree of ethoxylation: 3-50,alkyl radical: C₄-C₁₂), of alkylsulfonic acids (alkyl radical: C₁₂-C₁₈)and of alkylarylsulfonic acids (alkyl radical: C₉-C₁₈).

Useful cationic emulsifiers are generally C₆-C₁₈-alkyl-, C₆-C₁₈-aralkyl-or heterocyclyl-containing primary, secondary, tertiary or quaternaryammonium salts, alkanolammonium salts, pyridinium salts, imidazoliniumsalts, oxazolinium salts, morpholinium salts, thiazolinium salts andalso salts of amine oxides, quinolinium salts, isoquinolinium salts,tropylium salts, sulfonium salts and phosphonium salts. Examples whichmay be mentioned are dodecylammonium acetate or the correspondinghydrochloride, the chlorides or acetates of the various2-(N,N,N-trimethylammonium)ethyl paraffinic acid esters,N-cetylpyridinium chloride, N-laurylpyridinium sulfate and alsoN-cetyl-N,N,N-trimethylammonium bromide,N-dodecyl-N,N,N-trimethylammonium bromide,N,N-distearyl-N,N-dimethylammonium chloride and also the Geminisurfactant N,N-(lauryidimethyl)ethylenediamine dibromide. Numerousfurther examples may be found in H. Stache, Tensid-Taschenbuch,Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's,Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

Very particularly suitable emulsifiers include for example copolymers ofethylene and at least one α,β-unsaturated mono- or dicarboxylic acid orat least one anhydride of an α,β-unsaturated mono- or dicarboxylic acid,for example acrylic acid, methacrylic acid, crotonic acid, maleic acid,fumaric acid, methylenemalonic acid, maleic anyhdride, itaconicanhydride. The carboxyl groups can be partly or preferably whollyneutralized, for example with alkali metal ions, alkaline earth metalions, ammonium or amines, for example amines such as triethylamine,diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine,ethyldiisopropylamine, ethanolamine, diethanolamine, triethanolamine,N-methyldiethanolamine, N-(n-butyl)diethanolamine orN,N-dimethylethanolamine.

The fraction of emulsifier in the liquor can be chosen within widelimits and can be in the range from 0.1 to 100 g/l, preferably in therange from 0.2 to 10 g/l.

The process of the present invention is carried out by treating textilematerial with at least one aqueous liquor. It is possible to carry outplural treatment steps with identical or different liquors.

In one embodiment of the present invention, the process of the presentinvention comprises treating the textile first with a liquor whichcontains at least one organic polymer and further an organic orpreferably inorganic solid in particulate form and subsequently with anew liquor which comprises the organic polymer but no further organic orinorganic solid in particulate form.

In one embodiment of the present invention, the process of the presentinvention comprises treating the textile first with a liquor whichcomprises at least one organic polymer and further an organic orpreferably inorganic solid in particulate form and subsequently with anew liquor which comprises another organic polymer but no furtherorganic or inorganic solid in particulate form.

In one embodiment of the present invention, the process of the presentinvention comprises treating the textile first with a liquor whichcomprises at least one organic polymer and further an organic orpreferably inorganic solid in particulate form and subsequently with anew liquor which comprises no further polymer but does comprise theinorganic solid in particulate form already used in the first step.

The temperature at which the process of the present invention is carriedout is as such not critical. The liquor temperature can be in the rangefrom 10 to 60° C., preferably in the range from 15 to 30° C.

The process parameters for the process of the present invention can bechosen such that the process of the present invention will produce a wetpickup which is typically in the range from 25% by weight to 85% byweight and preferably in the range from 40% to 70% by weight.

The process of the present invention can be carried out in machinescommonly used for the finishing of textiles, for example pad-mangles.Preference is given to vertical textile feed pad-mangles, where theessential element is two rolls in press contact with each other, throughwhich the textile is led. The liquor is filled in above the rolls andwets the textile. The pressure causes the textile to be squeezed off andensures a constant add-on.

In one embodiment of the present invention, the speed of the pad-mangletextile feed is in the range from 1 to 40 m/min and preferably in therange from 1 to 30 m/min.

The treated textile after the treatment according to this invention canbe dried by methods customary in the textile industry.

The treatment according to the present invention can be followed by aheat treatment, which can be operated continuously or batchwise. Theduration of the heat treatment can be chosen within wide limits. Theheat treatment can typically be carried out for from about 10 seconds toabout 30 minutes, especially from 30 seconds to 5 minutes. The heattreatment is carried out by heating to temperatures of up to 180° C.,preferably up to 150° C. It is of course necessary to adapt thetemperature of the heat treatment to the sensitivity of the fabric.

An example of a suitable method of heat treatment is hot air drying;

In one embodiment of the present invention, the textile material isprovided with a bonding layer prior to the treatment according to thepresent invention. The bonding layer can be provided using a primer. Theapplication of a primer is preferable when synthetic dyed fibers are tobe finished.

In one embodiment of the present invention, the bonding layer applied tothe textile material to be treated can be for example one or morepolymers, in which case the polymer synthesis can also be carried out onthe textile material. Particularly useful polymers have crosslinked orcrosslinking-capable groups, for example natural or synthetic polymershaving free hydroxyl groups, carbonyl groups, primary or secondary aminogroups or thiol groups. Examples of very useful polymers are lignin,polysaccharides, polyvinyl alcohols and polyethyleneimine. Crosslinkingcan be accomplished for example by subsequent reaction with for exampleisocyanates, dimethylolurea or N,N-dimethylol-4,5-dihydroxyethyleneurea(DMDHEU). Other particularly preferred crosslinkers aremelamine-formaldehyde resins, which can have been etherified withmethanol.

In another embodiment, when polyesters or polyamides are to be treated,from 0.01% to 1% by weight and preferably from 0.1 to 0.5% by weight ofthe textile is saponified by partial saponification with strong alkalissuch as aqueous sodium hydroxide solution or potassium hydroxidesolution.

The present invention further provides textile materials finishedaccording to the process of the present invention. Finishing accordingto the present invention provides the textiles of the present inventionwith one or more coats. The textile materials of the present inventionexhibit particularly good soil- and water-repellent performance. Textilematerials according to the present invention further exhibit very goodmechanical strength. In the textile materials coated according to thepresent invention, the solid or solids used are isotropically orsubstantially isotropically distributed throughout the finishing coat,i.e., no concentration is observed in the boundary layer between thefinishing coat and the surrounding atmosphere.

In one embodiment, the textiles of the present invention comprise from0.5 to 50 g/m² of coating, preferably from 1 to 20 g/m² and morepreferably from 1.5 to 10 g/m².

The present invention further provides aqueous liquors for finishingtextile materials that comprise at least one organic polymer and atleast one organic or inorganic solid in particulate form, wherein theorganic or inorganic solids are present in the liquor in a fraction ofat least 5.5 g/l. The liquors of the present invention can comprisefurther components, for example one or more organic solvents or one ormore emulsifiers.

The present invention further provides for the use of the liquors of thepresent invention for finishing textile materials.

The present invention further provides a process for preparing aqueousliquors, hereinafter also referred to as preparation process of thepresent invention. The preparation process of the present inventioncomprises the mixing of the following components:

-   at least one organic polymer,-   at least one organic or inorganic solid in particulate form,-   water, and-   optionally one or more organic solvents,-   and optionally further components, for example one or more    emulsifiers,-   wherein the amount of organic or inorganic solid in particulate form    is chosen such that the organic or inorganic solid in particulate    form is present in the aqueous liquor in a fraction of at least 5.5    g/l.

The preparation process of the present invention can customarily becarried out at temperatures ranging from room temperature up to about100° C., room temperature being preferred.

The preparation process of the present invention comprises in general ahomogenizing step, for example by mechanical or pneumatic stirring,shaking, ultrasonication or a combination thereof. In some cases,however, the homogenizing step can be dispensed with.

The order in which the components are added is in principle freelychoosable. For instance, the first step can be to prepare a water- andsolvent-free mixture of polymer and organic or inorganic solid and thento disperse the dry mixture in organic solvent or mixture of water andorganic solvent or in water.

In one embodiment of the preparation process of the present invention,the initial step is to prepare formulations which comprise the organicpolymer, organic or inorganic solid in particulate form, optionally oneor more organic solvents and optionally one or more emulsifiers and alsooptionally water. Prior to performing the treatment of textile materialsin a manner according to the present invention, a liquor which is inaccordance with the present invention is then prepared by diluting theformulation with water. It is preferable that the formulations of thepresent invention comprise not more than 15% by weight, preferably about0.1-10% by weight, and more preferably up to 5% by weight of water. Theformulations of the present invention can also be water-free.

The present invention further provides formulations which compriseorganic polymer, organic or inorganic solid in particulate form,optionally one or more organic solvents and optionally one or moreemulsifiers and also optionally water, the fraction of water being inthe range from about 0.1% to 10% by weight and preferably about 5% byweight.

The examples which follow illustrate the invention.

EXAMPLE 1 Preparation of Inventive Liquors Example 1.1 Preparation ofLiquor 1.1

The following were mixed in a flask by mechanical stirring:

-   883.5 ml of demineralized water,-   62.4 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 10% by weight of methacrylic acid and    90% by weight of CH₂═C(CH₃)COO—CH₂—CH₂-n-C₈F₁₇ and having M_(n) 3000    g/mol (gel permeation chromatography),-   15.6 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 20% by weight of acrylic acid, 80% by    weight of ethylene, M_(w):-   20 000 g/mol, neutralized with N,N-dimethylethanolamine, pH between    8.5 and 9.5, and 25.2 g of isopropanol.

Then 13.3 g of dimethylsiloxane-modified pyrogenic silica having a BETsurface area of 225 m²/g, determined in accordance with German standardDIN 66131, primary particle diameter: 10 nm (median value, numberaverage) were added and dispersed in the mix for 10 minutes (Ultraturraxstirrer) to give the aqueous liquor 1.1.

Example 1.2 Preparation of Liquor 1.2

The following were mixed in a flask by mechanical stirring:

-   899.5 ml of demineralized water,-   52.4 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 10% by weight of methacrylic acid and    90% by weight of CH₂═C(CH₃)COO—CH₂—CH₂-n-C₆F₁₃ and having M_(n) 2900    g/mol (gel permeation chromatography),-   14.6 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 20% by weight of acrylic acid, 80% by    weight of ethylene, M_(w):-   20 000 g/mol, neutralized with N,N-dimethylethanolamine, pH between    8.5 and 9.5, and 25.2 g of isopropanol.

Then 8.3 g of trimethylsiloxane-modified pyrogenic silica having a BETsurface area of 200 m²/g were determined in accordance with Germanstandard DIN 66131, were added, primary particle size: 10 nm (medianvalue, number average), and dispersed in the mix for 10 minutes(Ultraturrax stirrer) to give the aqueous liquor 1.2.

Example 1.3 Preparation of Liquor 1.3

The following were mixed in a flask by mechanical stirring:

-   884.5 ml of demineralized water,-   66.3 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 10% by weight of methacrylic acid and    90% by weight of CH₂═C(CH₃)COO—CH₂—CH₂-n-C₈F₁₇ and having M_(n) 3000    g/mol (gel permeation chromatography),-   13.8 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 20% by weight of acrylic acid, 80% by    weight of ethylene, M_(w):-   20 000 g/mol, neutralized with N,N-dimethylethanolamine, pH between    8.5 and 9.5, and 30.2 g of isopropanol mixed by mechanical stirring.

Then 5.2 g of dimethylsiloxane-modified pyrogenic silica having a BETsurface area of 225 m²/g, determined in accordance with German standardDIN 66131, primary particle diameter: 10 nm (median value, numberaverage) were added and dispersed in the mix for 10 minutes (Ultraturraxstirrer) to give the aqueous liquor 1.3.

Example 1.4 Preparation of Liquor 1.4

The following were mixed in a flask by mechanical stirring:

-   886.3 ml of demineralized water,-   20.8 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 10% by weight of methacrylic acid and    90% by weight of CH₂═C(CH₃)COO—CH₂—CH₂-n-C₆F₁₃ and having M_(n) 3000    g/mol (gel permeation chromatography),-   57 g of an aqueous dispersion (solids content 20% by weight) of a    random copolymer formed from 20% by weight of acrylic acid, 80% by    weight of ethylene, M_(w):-   25 000 g/mol, neutralized with N,N-dimethylethanolamine, pH between    8.5 and 9.5, and 28.4 g of isopropanol.

Then 7.5 g of dimethylsiloxane-modified pyrogenic silica having a BETsurface area of 225 m²/g, determined in accordance with German standardDIN 66131, were added, primary particle size: 10 nm (median value,number average),

-   and dispersed in the mix for 10 minutes (Ultraturrax stirrer) to    give the aqueous liquor 1.4.

EXAMPLE 2 Textile Finishing Example 2.1

A woven polyester fabric having a basis weight of 220 g/m² was treatedwith liquor 1.1 on a pad-mangle from Mathis (model HVF12085). Thesqueeze pressure of the rolls was 2.6 bar. This produced a wet pickup of60%. The application speed was 2 m/min. The treated polyester fabric wassubsequently dried on a tenter at 120° C. The conclusive heat treatmenttook 3 min at 150° C. with circulating air. The treated polyester fabric2.1 was obtained.

Example 2.2

A woven polyamide fabric having a basis weight of 160 g/m² was treatedwith liquor 1.1 on a pad-mangle from Mathis (model HVF12085). Thesqueeze pressure of the rolls was 2.6 bar. This produced a wet pickup of65%. The application speed was 2 m/min. The treated polyamide fabric wassubsequently dried on a tenter at 120° C. The conclusive heat treatmenttook 3 min at 150° C. with circulating air. The treated polyamide fabric2.2 was obtained.

Example 2.3

A woven polyacrylic fabric having a basis weight of 295 g/m² was treatedwith liquor 1.1 on a pad-mangle from Mathis (model HVF12085). Thesqueeze pressure of the rolls was 2.6 bar. This produced a wet pickup of50%. The application speed was 2 m/min. The treated polyacrylic fabricwas subsequently dried on a tenter at 120° C. The conclusive heattreatment took 3 min at 150° C. with circulating air. The treatedpolyester fabric 2.3 was obtained.

Example 2.4

A woven polyester fabric having a basis weight of 220 g/m² was treatedwith liquor 1.2 on a pad-mangle from Mathis (model HVF12085). Thesqueeze pressure of the rolls was 2.6 bar. This produced a wet pickup of60%. The application speed was 2 m/min. The treated polyester fabric wassubsequently dried on a tenter at 120° C. The conclusive heat treatmenttook 3 min at 150° C. with circulating air. The treated polyester fabric2.4 was obtained.

Example 2.5

A woven polyamide fabric having a basis weight of 160 g/m² was treatedwith liquor 1.2 on a pad-mangle from Mathis (model HVF12085). Thesqueeze pressure of the rolls was 2.6 bar. This produced a wet pickup of65%. The application speed was 2 m/min. The treated polyamide fabric wassubsequently dried on a tenter at 120° C. The conclusive heat treatmenttook 3 min at 150° C. with circulating air. The treated polyamide fabric2.5 was obtained.

Example 2.6

A woven polyacrylic fabric having a basis weight of 295 g/m² was treatedwith liquor 1.2 on a pad-mangle from Mathis (model HVF12085). Thesqueeze pressure of the rolls was 2.6 bar. This produced a wet pickup of50%. The application speed was 2 m/min. The treated polyacrylic fabricwas subsequently dried on a tenter at 120° C. The conclusive heattreatment took 3 min at 150° C. with circulating air. The treatedpolyester fabric 2.6 was obtained.

3. Water Repellency Testing of textile Samples which have been TreatedAccording to the Present Invention

The textile sample which has been treated according to the presentinvention and is to be tested was manually tensioned and fixed withnails to a flat wooden board whose inclination was continuouslyadjustable in the range from 1° to 90°. A cannula was then used to dropindividual water droplets onto the textile sample from a height of 10mm. The droplets had a mass of 4.7 mg. The angle of inclination wasincrementally increased to that angle of inclination at which thedroplets were just starting to be beaded off and there was no sign ofadhesion. The results are given in Table 1.

TABLE 1 Angle of inclination Sample Angle of inclination [°] 2.1 5 2.2 32.3 6 2.4 7 2.5 6 2.6 8

1. A process for finishing textile materials comprising treating thetextile materials with at least one aqueous liquor which comprises atleast one organic polymer, at least one organic or inorganic solid inparticulate form having a median (number average) particle diameter inthe range from 1 nm to 350 nm, at least one emulsifier comprising atleast one copolymer of ethylene and at least one α,β-unsaturatedcarboxylic acid or at least one anhydride of an α,β-unsaturated mono- ordicarboxylic acid, wherein the at least one organic or inorganic solidis present in the liquor in a fraction of at least 5.5 g/l.
 2. Theprocess according to claim 1, wherein the at least one organic orinorganic solid is hydrophobic.
 3. The process according to claim 1,wherein the surface of the textile materials is provided with a bondinglayer prior to said treating.
 4. The process of claim 1, wherein the atleast one organic or inorganic solid comprises at least one inorganicsolid.
 5. The process according to claim 1, wherein the at least oneorganic or inorganic solid is present in the liquor in a fraction of atleast 7 g/l.
 6. The process according to claim 1, wherein the at leastone organic or inorganic solid comprises a particle diameter (medianvalue, number average) in the range from 1 to 350 nm.
 7. The processaccording to claim 1, wherein the at least one α,β-unsaturatedcarboxylic acid or the at least one anhydride of an α,β-unsaturatedmono- or dicarboxylic acid is selected from the group consisting ofacrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaricacid, methylenemalonic acid, maleic anyhdride, and itaconic anhydride.8. The process according to claim 1, wherein the fraction of emulsifierin the liquor is from 0.1 to 100 g/l.
 9. The process according to claim1, wherein the fraction of emulsifier in the liquor is from 0.2 to 10g/l.